CN113862035B - Method for producing high-end needle coke raw material from catalytic cracking slurry oil - Google Patents
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- 239000002002 slurry Substances 0.000 title claims abstract description 51
- 239000011331 needle coke Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000004523 catalytic cracking Methods 0.000 title claims description 32
- 239000002994 raw material Substances 0.000 title claims description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 239000012528 membrane Substances 0.000 claims abstract description 26
- 238000004821 distillation Methods 0.000 claims abstract description 16
- 230000008439 repair process Effects 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 8
- 239000012466 permeate Substances 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 239000007769 metal material Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 238000012856 packing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- 238000005899 aromatization reaction Methods 0.000 abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 239000000843 powder Substances 0.000 abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 abstract description 11
- 239000011593 sulfur Substances 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 4
- 238000005292 vacuum distillation Methods 0.000 abstract description 4
- 238000009295 crossflow filtration Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000011214 refractory ceramic Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 47
- 230000008569 process Effects 0.000 description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011162 core material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002956 ash Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004148 unit process Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- -1 asphaltene Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A process for preparing high-end needle coke from catalytically cracked oil slurry includes such steps as 1) filtering the catalytically cracked oil slurry by refractory ceramic membrane filter core or metal filter core, 2) vacuum distilling the filtered liquid, 3) mixing the intermediate fraction obtained by vacuum distillation with hydrogen, introducing it into hydrogenation reactor, hydrogenating, loading the resultant stream in desulfurizing catalyst unit, and loading it in hydroaromatizing repair catalyst unit. The invention adopts cross-flow filtration technology, which can effectively filter out catalyst fine powder and metal impurities; the effective components, namely the polycyclic aromatic hydrocarbon-rich components, can be reserved by adopting a reduced pressure distillation process; the method adopts a proper hydrogenation technology and a special hydrogenation catalyst to remove harmful elements such as sulfur, nitrogen and the like in the components, and retains the effective components for producing the high-end needle coke through the hydrogenation aromatization repair catalyst so as to meet the requirements for producing the high-end needle coke components.
Description
Technical Field
The invention relates to the field of petroleum processing, in particular to a method for treating catalytic cracking slurry oil.
Background
The catalytic cracking technology is one of three main processes of heavy oil deep processing, is a main process technology for lightening raw materials, and has strong adaptability to the raw materials. As catalytic cracker processing feedstocks become increasingly heavy, a number of disadvantages are introduced into catalytic cracker units. For example, the device may not operate properly due to coking and fouling; the distribution and quality of the product are affected; the light oil yield is reduced. In order to solve this problem, many refineries generally adopt an external slurry oil removal method. The amount of the external oil slurry in China accounts for 5% -10% of the treatment amount of the catalytic cracking device, and the amount of the external oil slurry per year is more than 500 ten thousand tons. The catalytic cracking slurry oil has high density, high carbon residue value, high viscosity and high aromatic content, contains residual catalyst particles and is difficult to use, so how to process and use the catalytic cracking slurry oil is an urgent problem to be solved by refineries.
The needle coke is a high-quality carbon raw material which is greatly developed in the 70 s of the 20 th century, and a graphite product prepared from the needle coke has the characteristics of high density, high strength, high purity, high crystallinity, high electric conductivity and thermal conductivity, low thermal expansion coefficient, low ablative property and the like, and is mainly used for producing high-power and ultra-high-power graphite electrodes for electric furnace steelmaking. In the metallurgical industry, the ultra-high power (UHP) graphite electrode made of needle coke can shorten the smelting time of electric furnace steelmaking by 50-70%, reduce the electricity consumption by 20-50%, remarkably improve the smelting efficiency, reduce the electricity consumption and raw material consumption, and reduce the environmental pollution. The research on the needle coke formation mechanism finds that the catalytic slurry oil of a refinery is a high-quality raw material for producing the needle coke, and the production of the needle coke by using the catalytic slurry oil greatly improves the added value of the product and simultaneously relieves the problem of shortage of needle coke resources in China.
Because the catalytic cracking slurry oil contains a certain amount of solid catalytic cracking catalyst powder and impurities such as higher sulfur, nitrogen, metal impurities and the like, needle coke cannot be directly produced, and harmful components are removed by further treatment to be used as raw materials for producing the needle coke.
The catalytic cracking slurry oil contains a certain amount of solid catalytic cracking catalyst powder and metal impurities, and slurry oil powder separation methods with better industrial application effects include a sedimentation separation method, an electrostatic separation method, a filtering separation method, a screening method, a liquid-solid suspension separation method and the like, but the removal effects of the methods on the catalyst powder and the metal impurities cannot meet the feeding requirement of a fixed bed hydrogenation reactor, otherwise, the fixed bed can generate the problems of pressure drop increase and blockage, and the long-period stable operation is difficult.
The catalytic slurry oil contains a certain light fraction, and also contains heavy fractions such as colloid, asphaltene and the like, and the heavy fractions seriously affect the quality of the high-end needle coke production and need to be removed. The production of high-quality needle coke is critical to the selection of raw materials, and requires low mass fractions of sulfur, nitrogen, asphaltene, ash, metal and other impurities and high aromatic hydrocarbon content, wherein tricyclic and tetracyclic aromatic hydrocarbons are mainly used.
Chinese patent CN110628461 a discloses a method for retaining aromatic hydrocarbon by selective hydrodesulfurization of slurry oil, which comprises the steps of firstly removing catalyst particles from slurry oil by ultrasonic-assisted centrifugation, wherein the mechanical action of the ultrasonic waves can effectively improve the removal effect of the catalyst particles; removing residual catalyst particles, asphaltene and colloid from the slurry oil, and retaining enriched aromatic hydrocarbonExtracting oil; then through selective hydrodesulfurization of the extracted oil, fe modified CoMo/gamma Al is utilized 2 O 3 The selective hydrodesulfurization catalyst desulfurizes.
Chinese patent CN103013567 a discloses a method for producing needle coke raw material from catalytic cracking slurry oil, which is provided with a protection zone and a hydrogenation reaction zone, wherein the catalytic cracking slurry oil firstly enters the protection zone to adsorb most of catalytic cracking catalyst powder, then is mixed with hydrogen into a heating furnace, and enters the hydrogenation reaction zone to carry out hydrogenation treatment reaction after heating. The invention sets a protection zone in front of the hydrogenation reaction zone, which can filter out most of catalytic cracking catalyst powder carried in the catalytic cracking slurry oil, thus achieving the purpose of protecting the hydrogenation main catalyst and realizing long-period operation. In addition, the sulfur in the catalytic cracking slurry oil is mostly removed by the catalytic cracking slurry oil hydrofinishing, and qualified needle coke raw materials are produced.
The two patent technologies can produce common grade needle coke raw materials, but the improvement is needed for producing high-end needle coke raw materials because the high-end needle coke raw materials require lower ash, sulfur and nitrogen contents and higher aromatic hydrocarbon contents.
Disclosure of Invention
The invention aims to provide a method for producing high-end needle coke raw materials from catalytic cracking slurry oil, which can efficiently remove dust and metal impurities of the catalytic cracking slurry oil catalyst, deeply desulfurize and retain aromatic components.
The method comprises the following specific contents:
1. the catalytic cracking slurry oil (FCC slurry oil) is filtered by a high temperature resistant ceramic membrane filter element or a metal material membrane filter element cross-flow filter to remove catalyst fine powder and metal impurities, and the pore diameter of the membrane is as follows: 1.2-0.05 mu m to adapt to slurry oil with the particle distribution of 0.01-200 mu m and the peak value of 10-40 mu m. Operating conditions for filtration: the temperature is 190-300 ℃; the pressure is 0.4-2.0 Mpa. The high temperature resistant special ceramic membrane filter core or metal material membrane filter core cross flow filter is a cross flow type filtering device, under the drive of pressure, the filtering medium flows in the membrane tube at high speed, small molecular substances permeate the membrane to become permeate, solid particles and macromolecular substances are intercepted, thus the purposes of separating, concentrating and purifying the fluid are achieved, and the ash content of the filtered slurry oil is less than 50ppm.
2. And (3) carrying out reduced pressure distillation on the filtered permeate liquid, and retaining an effective component, namely a polycyclic aromatic hydrocarbon-rich component, to remove light components, colloid, asphaltene and other useless components. And simultaneously, the scale of subsequent hydrogenation can be reduced. The conditions for the operation of the reduced pressure distillation are: the temperature of the slurry oil entering the tower is 300-350 ℃, the pressure of the tower top is 5-30 Kpa, the temperature of the tower top is 200-220 ℃, the temperature of the tower bottom is 280-300 ℃, and the middle distillate with the temperature of 300-450 ℃ is taken.
3. The middle fraction obtained by reduced pressure distillation is mixed with hydrogen and then is led into a hydrogenation reactor for hydrogenation treatment, the volume ratio of hydrogen to oil is 800-1000:1, two units are divided into the hydrogenation reactor, and according to the direction of reactant flow, the upper unit is filled with a hydrodesulfurization catalyst and the lower unit is filled with a hydrogenation aromatization repair catalyst. The reactant flow firstly enters a desulfurization catalyst unit in a hydrogenation reactor, and the filled hydrodesulfurization catalyst is gamma-Al 2 O 3 The catalyst is a hydrodesulfurization catalyst taking molybdenum and nickel as active components, wherein the active components of the catalyst comprise 0.5 to 15 percent of molybdenum (mass ratio) and 0.5 to 8 percent of nickel (mass ratio) calculated by oxide, and the balance of gamma-Al 2 O 3 A carrier. The filling volume percentage of the hydrodesulfurization catalyst in the hydrogenation reactor is 70-90%. Sulfur, nitrogen, and other elements in the middle distillate are removed by the catalyst of the unit. The reactant flow enters a hydrogenation reactor to be added with a hydrogenation aromatization repair catalyst unit, and the filled hydrogenation aromatization repair catalyst takes alumina and ZSM-5 molecular sieve as carriers, wherein the content of the alumina is 10-85% (mass ratio), and the content of the ZSM-5 molecular sieve is 10-85% (mass ratio); the hydrogenation aromatization repair catalyst with the active components of iron and zinc can repair aromatic hydrocarbon and increase the content of tricyclic and tetracyclic aromatic hydrocarbon, wherein the content of the active components of iron and zinc (ferric oxide) is 1-5% (mass ratio) and the content of zinc is 0.5-7% (mass ratio) in terms of oxide. The filling volume percentage of the hydrogenation aromatization repair catalyst in the hydrogenation reactor is 10-30%. Then the following hydrogenation operation is adopted, and the inlet pressure is 3.5-4.0 MpaThe initial reaction temperature is 330-350 ℃, the final reaction temperature is 360-380 ℃ and the volume space velocity is 0.8-1.0/h -1 . After passing through the hydrogenation reactor, sulfur and nitrogen compounds in the catalytic cracking slurry oil can be effectively removed, and polycyclic aromatic hydrocarbon is reserved at the same time, so that needle coke raw materials with various indexes meeting the requirements are obtained.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts the cross-flow filtration technology of the high temperature resistant ceramic membrane filter core or the metal material membrane filter core, can effectively filter out catalyst fine powder and metal impurities, prevent subsequent reduced pressure distillation and coking of a hydrogenation unit, protect hydrogenation catalyst and reduce ash content of needle coke raw materials;
2. the invention adopts a reduced pressure distillation process, can retain the effective components, namely the components rich in polycyclic aromatic hydrocarbon, cut off the light components and the non-ideal components such as colloid, asphaltene, and the like, and improve the production efficiency of the hydrogenation unit; the obtained light component is taken as a blending component extraction device such as wax oil and the like; the residual slurry oil residue component at the bottom of the tower is rich in colloid and asphaltene, and is properly blended with the oxidized asphalt to be sold as road asphalt, so that the product upgrading of the catalytic slurry oil is realized, and the economic benefit is improved.
3. The invention adopts proper hydrogenation technology and special hydrogenation catalyst to remove sulfur, nitrogen and other harmful elements in the components, and the catalyst is repaired by hydrogenation aromatization to keep the effective components for producing the high-end needle coke, especially tricyclic and tetracyclic aromatic hydrocarbon, thereby meeting the requirements for producing the high-end needle coke components.
Drawings
FIG. 1 is a schematic and schematic flow chart of the present invention.
In the schematic flow diagram of the invention shown in fig. 1, catalytic cracking slurry oil from a slurry oil storage tank 1 enters a high temperature resistant ceramic membrane filter element or a metal material membrane filter element cross-flow filter 2 after being heated, solid particles and macromolecular substances are trapped in a membrane pipe and circulate between the slurry oil storage tank and the high temperature resistant ceramic membrane filter element or the metal material membrane filter element cross-flow filter through a pipeline 3, and when the catalyst fine powder content in the circulating slurry oil reaches 7500-8500 mug/g, part of slurry oil is thrown out through a pipeline 4, so that the catalyst fine powder content in the circulating slurry oil is maintained at 500-8500 mug/g. The micromolecular substances in the membrane tube permeate the membrane to become permeate, and the permeate enters a vacuum distillation tower 6 through a pipeline 5 for vacuum distillation, light fraction in the vacuum distillation tower is discharged from the top of the tower through a pipeline 7, heavy fraction colloid and asphaltene are discharged from the bottom of the tower through a pipeline 8, and middle fraction is mixed with a hydrogen pipeline 14 through a pipeline 9 in the middle of the tower and then enters from the top of the hydrogenation reactor 10. The hydrogenation reactor is divided into an upper unit and a lower unit, wherein the upper unit is filled with a hydrodesulfurization catalyst 11, the lower unit is filled with a hydrogenation aromatization repair catalyst 12, and a high-end needle coke raw material (i.e. an effective component) 13 is discharged from the bottom of the hydrogenation reactor.
Detailed Description
The following examples further illustrate the invention but are not intended to limit it.
The feedstock used in the examples below, namely, a catalytic cracking (FCC) slurry, is shown in Table 1 below for its main indices
TABLE 1 catalytic cracking slurry feed
As can be seen from Table 1, the sulfur content, ash content and gum/pitch content of the catalytic cracking slurry oil are all high, and do not meet the requirements of producing needle coke raw materials.
Specific embodiments of the invention are as follows:
example 1
Taking the catalytic cracking slurry oil raw material shown in table 1, filtering by adopting a high temperature resistant ceramic membrane filter core cross-flow filter, wherein the membrane pore diameter is as follows: 1.2 μm, 190 ℃ and 0.4Mpa, and the permeate obtained after filtration is subjected to heat exchange and then enters a tower to be subjected to reduced pressure distillation at 300 ℃ under the following operation conditions: the pressure at the top of the column is 5Kpa, the temperature at the top of the column is 200 ℃, the temperature at the bottom of the column is 280 ℃, and the middle distillate at 300-450 ℃ is taken. Mixing the middle fraction obtained by reduced pressure distillation with hydrogen, introducing into a hydrogenation reactor for hydrogenation treatment, wherein the volume ratio of hydrogen to oil is 800:1, dividing the hydrogenation reactor into an upper unit and a lower unit, and filling the upper unit with a hydrodesulfurization catalyst and filling the lower unit with a hydrogenated aromatic structure in sequence according to the direction of a reactant flowAnd (5) chemically repairing the catalyst. The upper unit-packed hydrodesulfurization catalyst into which the reactant stream first enters is a catalyst that is gamma-Al 2 O 3 As carrier, molybdenum and nickel are used as active components of the hydrodesulfurization catalyst, the active components of molybdenum and nickel are calculated by oxide, the content of molybdenum is 15 percent (mass ratio), the content of nickel is 0.5 percent (mass ratio), and gamma-Al is calculated by mass ratio 2 O 3 The content of carrier was 84.5%. The loading volume percent of the hydrodesulfurization catalyst in the hydrogenation reactor is 90%. The reactant flow enters a lower unit to be filled, wherein the content of alumina is 10 percent (mass ratio), a ZSM-5 molecular sieve is 84.5 percent (mass ratio) and is used as a carrier, and the metal active components are iron and zinc hydrogenation aromatization repair catalyst, wherein the active components are iron and zinc in terms of oxide, the content of iron (ferric oxide) is 5 percent (mass ratio), and the content of zinc is 0.5 percent (mass ratio). The loading volume percentage of the hydrogenation aromatization catalyst in the hydrogenation reactor is 10 percent. Then the hydrogenation operation conditions are that the inlet pressure is 3.5Mpa, the initial reaction temperature is 330 ℃, the final reaction temperature is 360 ℃ and the volume space velocity is 0.8/h -1 Finally, needle coke raw material products are obtained, and various performance indexes are shown in Table 5.
Example 2
The same catalytic slurry feed and treatment process as in example 1 was used, wherein a high temperature resistant metal membrane filter core cross flow filter was used for filtration, the membrane pore size was: 0.05 μm, operating process conditions are shown in Table 2; the operating conditions for reduced pressure distillation are shown in Table 3; mixing the middle fraction obtained by reduced pressure distillation with hydrogen, introducing into a hydrogenation reactor for hydrogenation treatment, wherein the volume ratio of hydrogen to oil is 1000:1, the middle upper part of the hydrogenation tower is filled with a hydrogenation catalyst, the contents of molybdenum and nickel in the catalyst are respectively 0.5% and 8%, and the carrier is gamma-Al 2 O 3 The content of (2) is 91.5%, the filling amount in the tower is 70%, and the aromatic hydrocarbon-rich fraction is used for removing sulfur, nitrogen and other elements through the layer; the lower middle part of the hydrogenation tower is filled with a hydrogenation aromatization repair catalyst, the contents of iron and zinc are respectively 1% and 7%, the carrier is 82% of alumina (mass ratio), the ZSM-5 molecular sieve is 10% of the carrier, and the filling amount of the tower is 30%. Other operating conditions are shown in Table 4; the process can meet the requirements of producing high-end needle coke components, and the product propertyThe quality is shown in Table 5.
Example 3
The same catalytic slurry feed and treatment process as in example 1 was used, wherein a high temperature resistant ceramic membrane filter core cross flow filter was used for filtration, the membrane pore size was: 0.1 μm, operating process conditions are shown in Table 2; the operating conditions for reduced pressure distillation are shown in Table 3; mixing the middle fraction obtained by reduced pressure distillation with hydrogen, introducing into a hydrogenation reactor for hydrogenation treatment, wherein the volume ratio of hydrogen to oil is 900:1, the middle upper part of the hydrogenation tower is filled with a hydrogenation catalyst, the contents of molybdenum and nickel in the catalyst are respectively 3% and 4%, and the carrier is gamma-Al 2 O 3 The content of the catalyst is 93.0%, the filling amount of the tower is 80%, and the aromatic hydrocarbon-rich fraction is used for removing sulfur, nitrogen and other elements through the layer; the lower middle part of the hydrogenation tower is filled with a hydrogenation aromatization repair catalyst, the contents of iron and zinc are respectively 2 percent and 5 percent, the carrier is 50 percent (mass ratio) of alumina, the 43 percent (mass ratio) of ZSM-5 molecular sieve is the carrier, and the filling amount in the tower is 20 percent. Other operating conditions are shown in Table 4; the above process can meet the requirements of producing high-end needle coke components, and the properties of the product are shown in Table 5.
TABLE 2 Cross-flow Filter Process conditions
TABLE 3 reduced pressure distillation unit process conditions
TABLE 4 hydrogenation unit process conditions
TABLE 5 product fraction Properties
Claims (4)
1. A method for producing high-end needle coke raw materials from catalytic cracking slurry oil, which is characterized in that:
1) The catalytic cracking slurry oil is filtered by a high temperature resistant ceramic membrane filter core or a metal material membrane filter core cross-flow filter, and the pore diameter of the membrane is as follows: 1.2-0.05 mu m;
2) Performing reduced pressure distillation on the filtered permeate;
3) Mixing the middle fraction obtained by reduced pressure distillation with hydrogen, introducing the mixture into a hydrogenation reactor for hydrogenation treatment, wherein the volume ratio of hydrogen to oil is 800-1000:1, dividing the hydrogenation reactor into two units, introducing the reactant flow into a desulfurization catalyst unit in the hydrogenation reactor, and filling the desulfurization catalyst which is gamma-Al 2 O 3 The catalyst is a hydrodesulfurization catalyst taking molybdenum and nickel as active components, wherein the active components of the catalyst comprise 0.5 to 15 mass percent of molybdenum, 0.5 to 8 mass percent of nickel and the balance of gamma-Al in terms of oxide 2 O 3 The loading volume percentage of the carrier in the hydrogenation reactor of the hydrodesulfurization catalyst is 70-90%; the reactant flow enters a hydrogenation reactor to be added with a hydroaromatization repair catalyst unit, the packed hydroaromatization repair catalyst takes alumina and ZSM-5 molecular sieve as carriers, the active components are iron and zinc, wherein the mass content of the alumina is 10-85%, the mass content of the ZSM-5 molecular sieve is 10-85%, the active components are iron and zinc in terms of oxide, the oxide of the iron is ferric oxide, the mass content of the ferric oxide is 1-5%, the mass content of the zinc is 0.5-7%, and the packing volume percentage of the hydroaromatization repair catalyst in the hydrogenation reactor is 10-30%.
2. The method for producing high-end needle coke feedstock from catalytic cracking slurry oil according to claim 1, characterized in that: operating conditions for filtration: the temperature is 190-300 ℃; the pressure is 0.4-2.0 Mpa.
3. The method for producing high-end needle coke feedstock from catalytic cracking slurry oil according to claim 1, characterized in that: the conditions for the operation of the reduced pressure distillation are: feeding the mixture into a tower at 300-350 ℃, the tower top pressure of 5-30 Kpa, the tower top temperature of 200-220 ℃, the tower bottom temperature of 280-300 ℃, and taking middle distillate at 300-450 ℃.
4. The method for producing high-end needle coke feedstock from catalytic cracking slurry oil according to claim 1, characterized in that: the hydrogenation operation conditions are as follows, the inlet pressure is 3.5-4.0 Mpa, the initial reaction temperature is 330-350 ℃, the final reaction temperature is 360-380 ℃ and the volume airspeed is 0.8-1.0/h -1 。
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